JP3873943B2 - Plasma monitoring method, plasma processing method, semiconductor device manufacturing method, and plasma processing apparatus - Google Patents

Description

  The present invention relates to a plasma monitoring method, a plasma processing method, a semiconductor device manufacturing method, and a plasma processing apparatus that can detect specific radicals with high accuracy.

  In recent developments of ULSI devices, various companies are studying with the realization of high speed and low power consumption in mind. Under such circumstances, multilayer wiring technology using a low dielectric constant material film (so-called low-k film) and copper (Cu) has become common, and ensuring wiring reliability has become a very important issue. ing.

For example, in the process of using a SiOCH-based low dielectric constant material as an interlayer insulating film, as shown in FIG. 6A, the SiOCH-based film 102 and the SiO ₂ film 103 on the substrate 101 and the resist 104 as a mask are used. After the groove 105 is formed by the etching used, an ashing process for removing the resist 105 is performed. In this ashing step, ashing damage may be applied to the SiOCH-based film 102 and an oxide layer 106 may be formed on the sidewall of the groove 105. This is presumably because the material of the SiOCH-based film 102 is very unstable, and oxidation proceeds easily due to the presence of excess oxygen (O) radicals or the like. In the state where such ashing damage is applied, as shown in FIG. 6B, when wet processing is performed as post-processing, the oxide layer 106 is scraped, and unnecessary dimensional conversion differences or steps on the side walls of the grooves 105 are obtained. It has been reported that the desired characteristics cannot be obtained in the Cu wiring (not shown) embedded in the groove 105.

  For this reason, in the ashing process described above, establishment of a technique for suppressing ashing damage while removing a resist pattern made of an organic material is required. For this purpose, it is necessary to accurately monitor the amount of oxygen (O) radicals in the ashing process.

  Conventionally, the actinometry method has been applied to monitor the amount of O radicals. This actinometry method is a method for obtaining the absolute value of the O radical amount from the ratio between the emission intensity of oxygen and the emission intensity of argon (Ar) introduced together with oxygen (see Non-Patent Document 1 below).

“Plasma Source Sci. Technol.” (English), 1994, Vol. 3, p. 154-161

  However, the actinometry method described above cannot accurately monitor the amount of O radicals. FIG. 7 shows a graph in which the horizontal axis represents the amount of oxygen radicals determined by the actinometry method and the vertical axis represents the ashing rate of the resist. Here, the ashing rate of the resist should be an amount proportional to the amount of O radicals, but the O radical concentration determined by the actinometry method is not a value proportional to the ashing rate, It can be seen that an accurate O radical concentration cannot be monitored.

This is because, in spite of the fact that the emission intensity of oxygen (wavelength λ = 777 nm) usually measured includes not only O atom radical emission but also dissociative emission of oxygen molecules (O ₂ ), the actinometry method This is for determining the O radical concentration by regarding the measured emission intensity at the wavelength λ = 777 nm as the emission of only O radicals.

  Accordingly, the present invention provides a plasma monitoring method capable of monitoring a specific atomic radical amount with high accuracy and a simple method, a plasma processing method capable of reliably performing processing control, a semiconductor device manufacturing method, and An object of the present invention is to provide a plasma processing apparatus.

  The plasma monitoring method of the present invention for achieving such an object is caused by dissociation of the molecular source gas during the plasma processing performed by introducing the molecular source gas and the rare gas into the processing atmosphere. Monitoring method for detecting the amount of atomic radicals, and the molecular pressure of the molecular source gas in the processing atmosphere, the emission intensity of the rare gas, and the partial pressure of the rare gas in the processing atmosphere. It is characterized in that the degree of dissociation of the organic source gas is obtained and the amount of the atomic radical is predicted from the degree of dissociation.

  Originally, the atomic radical amount is a value that should be proportional to the treatment rate. It has now been found that the degree of dissociation of molecular source gas is very well proportional to the processing rate in plasma processing.

  Specifically, the dissociation degree of the molecular raw material gas is determined by the dissociation degree E = the partial pressure P1 of the molecular raw material gas, the emission intensity I of the rare gas, and the partial pressure P2 of the rare gas in the processing atmosphere. It is calculated as P1 × (I / P2). In FIG. 1, in the ashing process (plasma process) when oxygen molecular gas is used as the molecular source gas and argon is used as the rare gas, the dissociation degree E of the oxygen molecular gas thus obtained is plotted on the horizontal axis. The graph which took the ashing rate (processing rate) on the vertical axis | shaft is shown. As shown in this graph, it can be seen that the dissociation degree E obtained by the present invention is a highly accurate value that is very well proportional to the ashing rate (that is, the amount of oxygen radicals).

  Therefore, by predicting the amount of atomic radicals from the degree of dissociation that is very well proportional to the treatment rate in this way, the amount of atomic radicals can be accurately determined without being influenced by other light emission factors such as dissociative light emission. Will be predicted.

  The present invention is also a plasma processing method for controlling processing conditions so that the atomic radical amount determined by such a plasma monitoring method becomes a predetermined atomic radical amount. Furthermore, the present invention is also a method for manufacturing a semiconductor device in which a substrate surface is processed by such plasma processing.

  In such a plasma processing method, plasma processing is performed while accurately controlling the amount of atomic radicals in the processing atmosphere. Therefore, the process which prevented generation | occurrence | production of an excessive radical or controlled the processing rate with high precision is performed.

  And in the manufacturing method of the semiconductor device which performs such a plasma process, the process with favorable shape precision is performed by the process by which the damage by excess radical was prevented or the process rate was controlled with high precision.

  Furthermore, the present invention is a plasma processing apparatus for performing the above-described plasma processing method, and includes a processing chamber in which plasma processing is performed, and a light emission detecting means for detecting light emission of a specific wavelength in the processing chamber. . Furthermore, the molecular source gas is generated by dissociation from the emission intensity of the rare gas measured by the luminescence detection means, the density of the rare gas in the processing chamber, and the partial pressure of the molecular source gas in the processing chamber. Calculation means for obtaining the atomic radical amount of the atom is provided, and process control means for controlling processing conditions based on the atomic radical amount obtained by the calculation means.

  According to the plasma processing apparatus having such a configuration, the above-described plasma processing of the present invention is performed.

  As described above, according to the plasma monitoring method of the present invention, the amount of atomic radicals is predicted from the degree of dissociation that is very proportional to the processing rate, and thus depends on other light emission factors such as dissociative light emission. Therefore, it is possible to predict the atomic radical amount with good accuracy. In addition, according to the plasma processing method of the present invention, by controlling the processing conditions based on the atomic radical amount predicted by such a monitoring method, generation of excessive radicals can be prevented, or the processing rate can be increased with high accuracy. It is possible to perform controlled processing. Then, according to the method for manufacturing a semiconductor device of the present invention that performs such a plasma processing method, damage due to excessive radicals is prevented, or processing with good shape accuracy is performed by processing whose processing rate is controlled with high accuracy. It becomes possible. Furthermore, according to the plasma processing apparatus of the present invention, the above-described plasma processing of the present invention can be performed.

  Hereinafter, embodiments of the present invention will be described in detail in order from the plasma processing method.

<Plasma monitor method>
The plasma monitoring method described in the embodiment is a plasma that detects the amount of atomic radicals generated by dissociation of a molecular source gas during plasma processing performed by introducing a molecular source gas and a rare gas into the processing atmosphere. It is a monitoring method.

Here, the molecular source gas is an oxygen molecule (O ₂ ), a hydrogen molecule (H ₂ ), a nitrogen molecule (N ₂ ), water (H ₂ O), ammonia (NH ₃ ), etc. A gas suitable for the purpose is used.

  On the other hand, the rare gas is selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe) according to the molecular source gas. In particular, in the plasma treatment that performs the monitoring method of the present embodiment, among the rare gases, a gas having a light emission collision cross section that can emit light with energy given when dissociating the molecular source gas to obtain atomic radicals is used. To do. Further, it is preferable to use a noble gas having a light emission collision cross section that is closer to the dissociation collision cross section of the molecular source gas. The light emission collision cross section is the probability that an electron collides with an atom or molecule and shines, and is a function of energy. Similarly, the dissociation collision cross section is the probability that an electron collides with a molecule and dissociates, and is a function of energy.

In plasma processing, first, the emission intensity IAr of a rare gas (for example, Ar in this case) in the processing atmosphere is measured. In this method, only the emission intensity IAr of a specific rare gas is measured using a light emission detector and a spectroscope. Further, the partial pressure PO ₂ (P2) of the molecular source gas (for example, oxygen molecule O ₂ here) introduced into the processing atmosphere and the partial pressure PAr (P1) of the rare gas are obtained. These partial pressures PO ₂ and PAr are obtained from the flow rate of the rare gas introduced into the processing atmosphere, the flow rate of the molecular source gas, and the pressure in the processing atmosphere.

Then, from the emission intensity IAr of the rare gas, the partial pressure PO ₂ of the molecular source gas, and the partial pressure PA Ar of the rare gas, the dissociation degree EO ₂ of the molecular source gas (O ₂ ) is expressed by the following equation (1). Ask for. EO ₂ = PO ₂ × (IAr / PAr) (1)

  Here, the emission IAr of the rare gas (Ar) that does not dissociate is expressed by the following equation (2) using the partial pressure PAr of the rare gas, the electron density Ne, the above-described emission collision cross section σAr, and the electron energy v. It can be expressed as follows. IAr = PAr · Ne <σAr · v> (2) From this equation (2), (IAr / PAR) = Ne <σAr · v> in equation (1).

On the other hand, the dissociation of the molecular source gas (O ₂ ) is also a phenomenon caused by electron collision in the same manner as the light emission described above, and the degree of dissociation EO ₂ is the partial pressure PO ₂ of the molecular source gas, the electron density Ne, The dissociation collision cross section σO ₂ and the electron energy v can be used to express the following equation (3). EO ₂ = PO ₂ · Ne <σO ₂ · v> (3)

Therefore, by considering the dissociation collision cross section σO ₂ of the molecular source gas during the plasma treatment to be equivalent to the emission collision cross section σAr of the rare gas, Ne <σO ₂ · v> in the equation (3) is expressed as Ne < Replacing σAr · v> = (IAr / PAr) yields the above equation (1). Thus, in order to regard the dissociation collision cross section σO ₂ of the molecular source gas during plasma processing as equivalent to the emission collision cross section σAr of the rare gas, the light emission collision closer to the dissociation collision cross section of the molecular source gas By selecting a rare gas having a cross-sectional area, the numerical accuracy of the dissociation degree EO ₂ of the separable source gas is further improved.

Then, the amount of atomic radicals generated by the dissociation of the molecular source gas is predicted from the degree of dissociation EO ₂ of the molecular source gas obtained as described above.

FIG. 1 shows the dissociation amount E obtained as described above in the ashing process (plasma process) when oxygen molecular gas (O ₂ ) is used as the molecular source gas and argon (Ar) is used as the rare gas. A graph with (EO ₂ ) on the horizontal axis and the ashing rate proportional to the amount of O radicals on the vertical axis is shown. In this ashing process, each factor (pressure, power, flow rate) of the processing conditions is changed within the following range. Gas flow rate: O ₂ / Ar = 200/10 sccm to 5000/250 sccm, processing atmosphere pressure: 1 to 100 Pa, high frequency power (Power): 500 to 5000 W. However, the substrate temperature is 30 ° C.

  As shown in this graph, it can be seen that the dissociation amount E obtained by the present invention is a highly accurate value that is very well proportional to the ashing rate (that is, the amount of oxygen radicals). For this reason, it becomes possible to predict the amount of O radicals (amount of atomic radicals) with very high accuracy from the dissociation amount E thus obtained.

<Plasma treatment method>
In the plasma processing method of the embodiment, the plasma processing is performed while accurately controlling the atomic radical amount in the processing atmosphere based on the atomic radical amount predicted by the above-described plasma monitoring method, for example, the oxygen (O) radical amount. . In this case, the processing conditions are controlled so as to achieve a predetermined atomic radical amount or a predetermined processing rate.

  As a result, the amount of radicals (treatment rate) is controlled based on the amount of radicals (treatment rate) predicted with good accuracy, thereby preventing the generation of excessive radicals and increasing the treatment rate with high precision. Controlled plasma processing can be performed. As a result, it is possible to perform plasma processing with good shape accuracy, for example, without causing damage due to excessive radicals and controlling the processing amount with high accuracy.

<Plasma processing equipment>
FIG. 2 is a configuration diagram illustrating an example of a plasma processing apparatus for performing the above-described plasma processing method. Next, an embodiment of the plasma processing apparatus will be described with reference to this drawing.

  The plasma processing apparatus 1 shown in this figure includes a processing chamber 3 in which plasma processing is performed. In the processing chamber 3, a stage 4 for placing the substrate W to be processed is provided, and a voltage is applied to the stage 4. Further, the processing chamber 3 is provided with a gas introduction pipe 5 for introducing a processing gas into the processing chamber 3. The gas introduction pipe 5 has a flow rate for introducing a plurality of gases into the processing chamber 3 at a predetermined flow rate. A control unit 6 is provided. Further, a coil 7 for generating plasma in the processing chamber 3 is disposed on the outer periphery of the processing chamber 3. The above configuration is the same as that of a normal plasma processing apparatus, and is not limited to such a configuration as long as plasma processing can be performed in the processing chamber 3.

  Further, the plasma processing apparatus 1 is provided with a light emission detecting means 8 for detecting light emission of a specific wavelength in the processing chamber 3. The light emission detecting means 8 includes a light emission detection unit 8a for detecting light emission in the processing chamber 3, and a light spectral unit 8b detected by the light emission detection unit 8a.

  And the calculating means 9 is connected to this spectroscopy part 8b. This calculating means 9 is based on the partial pressure P1 of the molecular source gas in the processing chamber 3, the emission intensity I of the rare gas measured by the luminescence detection means 8, and the partial pressure P2 of the rare gas in the processing chamber 3. The degree of dissociation E of the molecular source gas is obtained, and the degree of dissociation E is calculated as described in the plasma monitoring method described above. The calculation means 9 obtains information on the partial pressure P1 of the molecular source gas in the processing chamber 3 and the partial pressure P2 of the rare gas in the processing chamber 3 from the process control means 10 described below. To do.

  The process control means 10 connected to the calculation means 9 is connected to the power source 7a of the coil 7, the flow rate control part 6, the exhaust part of the processing chamber 3 and the external input means not shown here. . Then, by adjusting the power source 7 a and the flow rate control unit 6, the processing conditions are controlled based on the atomic radical amount predicted from the dissociation degree E obtained by the calculation means 9. The processing conditions controlled here are, for example, the gas flow rate controlled by the flow rate control unit 6, the pressure in the processing chamber 3, and the high-frequency power (Power) applied from the power source 7a. At this time, the processing conditions are controlled such that the atomic radical amount becomes a predetermined atomic radical amount input and set from the external input means.

  According to such a plasma processing apparatus 1, the radical amount is controlled with high accuracy as described above by introducing the molecular source gas and the rare gas into the processing chamber 3 from the gas introduction pipe 5 while controlling the flow rates of the molecular raw material gas and the rare gas, respectively. Plasma treatment can be performed.

<Semiconductor Device Manufacturing Method-1>
Here, an embodiment in which the above-described plasma processing method is applied when holes are formed in the SiOCH film 33 which is a low dielectric constant film will be described as a first example of the manufacturing method.

First, as shown in FIG. 3A, a SiOCH film 33 is formed on a substrate 30 via a SiC film 31, and a SiO ₂ film 35 is further formed. Then, holes 39 are formed in the SiO ₂ film 35 and the SiOCH film 33 by etching using the resist 37 as a mask. Thereafter, an ashing process for removing the resist 37 used for the mask is performed as a plasma process.

In this ashing process, oxygen molecules (O ₂ ) are used as the molecular source gas, and argon (Ar) is used as the rare gas. Then, the dissociation amount EO ₂ of oxygen molecules (O ₂ ) is obtained, and the processing conditions are controlled so that the ashing rate (O radical amount) predicted from the dissociation amount EO ₂ is in the region A (see FIG. 1). While performing the ashing process. In this way, the ashing process is performed while controlling the processing conditions, thereby suppressing damage due to excessive O radicals.

  Next, as shown in FIG. 3B, wet processing using dilute hydrofluoric acid is performed as post-processing.

According to the above procedure, by performing the ashing process in a region where the ashing rate (O radical amount) predicted from the O ₂ dissociation amount EO ₂ is low, it is possible to reliably prevent the generation of excessive O radicals. Therefore, damage to the SiOCH film 33 due to excessive O radicals can be suppressed, and the altered layer thickness can be suppressed to 10 nm or less. As a result, the holes 39 can be formed in the SiOCH film 33 with good shape accuracy.

<Semiconductor Device Manufacturing Method-2>
Here, as in the first example, another embodiment in which the above-described plasma processing method is applied when holes are formed in the SiOCH film 33, which is a low dielectric constant film, will be described as a second example of the manufacturing method.

First, the holes 39 are formed in the SiO ₂ film 35 and the SiOCH film 33 in the same manner as described with reference to FIG.

Thereafter, an ashing process for removing the resist 37 used for the mask is performed as a plasma process. In this ashing process, hydrogen molecules (H ₂ ) that are less reactive than oxygen are used as the molecular source gas, and helium having a light emission collision cross section that is closer to the dissociation collision cross section of the hydrogen molecules (H ₂ ) as the rare gas. (He) is used. Even in such an ashing process using a gas system, the dissociation amount EH ₂ of the hydrogen molecule (H ₂ ), which is a molecular raw material gas, is very low in the ashing rate (that is, the H radical amount) within the range of the following processing conditions. It has been confirmed that it is proportional to Gas flow rate: H2 / He = 200/10 sccm to 5000/250 sccm, processing atmosphere pressure: 1 to 100 Pa, high frequency power (Power) 500 to 5000 W. However, the substrate temperature is 30 ° C.

Then, a dissociation amount EH ₂ of hydrogen molecules (H ₂ ) is obtained, and an ashing process is performed while controlling the processing conditions so that the ashing rate (H radical amount) predicted from the dissociation amount EH ₂ is low. . In this way, the ashing process is performed while controlling the processing conditions, thereby suppressing damage caused by excessive H radicals.

  After the above, as shown in FIG. 3 (2), the wet process using dilute hydrofluoric acid is performed as the post process as in the first example.

Even in such a method, by controlling the processing conditions by the ashing rate (the amount of H radicals) predicted from the dissociation amount EH _{2 of} H ₂ which is the molecular raw material gas, the generation of excess H radicals is ensured. Can be prevented. As a result, as in the first example, the hole 39 can be formed in the SiOCH film 33 with good shape accuracy.

<Semiconductor Device Manufacturing Method-3>
Here, an embodiment in which the above-described plasma processing method is applied to nitridation of a gate oxide film will be described as a third example of the manufacturing method.

First, as shown in FIG. 4A, a silicon oxide film 43 is formed on a silicon substrate 41. Then, by exposing the surface of the silicon oxide film 43 to nitrogen radicals, the surface of the silicon oxide film 43 is nitrided (plasma treated) with nitrogen radicals. In this nitriding process, using nitrogen molecules (N ₂₎ as the molecular raw material gas, a close helium (He) having a closer emitting collision cross section and dissociation collision cross section of nitrogen molecules (N ₂₎ as the rare gas . Even in the ashing process using such a gas system, the dissociation amount EN ₂ of the nitrogen molecule (N ₂ ), which is a molecular raw material gas, is very low in the ashing rate (that is, the amount of N radicals) within the range of the following conditions. It has been confirmed that it is in good proportion. Gas flow rate: N ₂ / He = 200/10 sccm to 5000/250 sccm, processing atmosphere pressure: 1 to 100 Pa, high frequency power (Power) 500 to 5000 W. However, the substrate temperature is 30 ° C. This is presumably because the nitridation of the oxide film depends on the supply of N radicals and the generation of dangling bonds for bonding.

Then, a dissociation amount EN ₂ of nitrogen molecules (N ₂ ) is obtained, and an ashing process is performed while controlling the processing conditions so that the nitriding rate (N radical amount) predicted from the dissociation amount EN ₂ is in a low region. . In this way, by performing the ashing process while controlling the processing conditions, damage due to excessive N radicals is suppressed.

  Thereby, a silicon nitride film 45 is formed on the surface layer of the silicon oxide film 43 as shown in FIG.

Even in such a way, by controlling the processing conditions by nitridation rate that is predicted from the dissociation amount EN ₂ of N ₂ is a molecular raw material gas (N radical amount), process controllability good nitriding Is possible.

<Method for Manufacturing Semiconductor Device-4>
Here, an embodiment in which the above-described plasma processing method is applied to processing of a multilayer resist will be described as a fourth example of the manufacturing method.

  First, as shown in FIG. 5A, a lower layer resist 53 is formed on a substrate 50 via silicon oxide 51, an SOG film 55 is further formed, and an upper layer resist 57 for ArF excimer laser light is patterned. To do. Then, the SOG film 55 is etched using the upper layer resist 57 as a mask.

  Thereafter, as shown in FIG. 5B, an etching process for pattern etching the lower resist 53 is performed as a plasma process using the SOG film 55 as a mask.

In this ashing process, as in the first example, oxygen molecules (O ₂ ) are used as the molecular source gas and argon (Ar) is used as the rare gas. Then, the amount of dissociation EO ₂ of oxygen molecules (O ₂ ) is obtained, and the etching process is performed while controlling the processing conditions so that the etching rate (O radical amount) predicted from the amount of dissociation EO ₂ becomes a predetermined etching rate. Do. Thereby, the side etch amount below the SOG film 55 is controlled. At this time, the processing conditions are controlled within a range of the following conditions. Gas flow rate: O2 / Ar = 500/50 sccm to 5000/250 sccm, processing atmosphere pressure: 1 to 100 Pa, high frequency power (Power) 500 to 5000 W. However, the substrate temperature is 30 ° C.

According to the above procedure, the side etching amount is controlled with high accuracy by performing the etching process while controlling the etching rate (O radical amount) predicted from the dissociation amount EO _{2 of} O ₂ . As a result, the lower layer resist 53 can be etched with good shape accuracy.

  Since the generation amount of atomic radicals can be accurately predicted, it can be widely applied to a manufacturing method in which high-precision plasma processing is performed.

It is a graph which shows the relationship between the dissociation degree of molecular source gas, and the processing rate proportional to the amount of atomic radicals. It is a block diagram of the plasma processing apparatus of embodiment. It is sectional process drawing explaining the 1st example and 2nd example of the manufacturing method of a semiconductor device. It is sectional process drawing explaining the 3rd example of the manufacturing method of a semiconductor device. It is sectional process drawing explaining the 4th example of the manufacturing method of a semiconductor device. It is sectional process drawing which shows an example of the manufacturing process of the semiconductor device to which the conventional plasma processing is applied. It is the graph which made the vertical axis | shaft the amount of oxygen radicals calculated | required by the actinometry method, and the ashing rate of a resist.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Plasma processing apparatus, 3 ... Processing chamber, 8 ... Light emission detection means, 9 ... Calculation means, 10 ... Process control means

Claims (6)

A plasma monitoring method for detecting the amount of atomic radicals generated by dissociation of the molecular raw material gas during plasma processing performed by introducing a molecular raw material gas and a rare gas into a processing atmosphere,
The degree of dissociation of the molecular source gas is determined from the partial pressure of the molecular source gas in the processing atmosphere, the emission intensity of the noble gas, and the partial pressure of the noble gas in the processing atmosphere. The amount of atomic radicals is predicted from the plasma monitoring method. The plasma monitoring method according to claim 1,
The degree of dissociation is determined by the degree of dissociation E = P1 × (I / P2) from the partial pressure P1 of the molecular source gas, the emission intensity I of the noble gas, and the partial pressure P2 of the noble gas in the processing atmosphere. The plasma monitoring method characterized by calculating | requiring by these. The plasma monitoring method according to claim 1,
As the rare gas, a rare gas having a light emission collision cross section closer to the dissociation collision cross section of the molecular source gas is used. A plasma processing method performed by introducing a molecular source gas and a rare gas into a processing atmosphere,
From the dissociation degree of the molecular source gas determined from the partial pressure of the molecular source gas in the processing atmosphere, the emission intensity of the noble gas, and the partial pressure of the noble gas in the processing atmosphere, the atoms Predict the amount of radicals,
Process conditions are controlled so that the amount of atomic radicals becomes a predetermined amount of atomic radicals. A method for manufacturing a semiconductor device for processing a substrate surface by plasma treatment,
A molecular source gas and a rare gas are introduced into a processing atmosphere for plasma processing,
From the dissociation degree of the molecular source gas determined from the partial pressure of the molecular source gas in the processing atmosphere, the emission intensity of the noble gas, and the partial pressure of the noble gas in the processing atmosphere, the atoms Predict the amount of radicals,
The method of manufacturing a semiconductor device, wherein the plasma processing is performed while controlling processing conditions such that the atomic radical amount becomes a predetermined atomic radical amount. A processing chamber in which plasma processing is performed, and
Light emission detection means for detecting light emission of a specific wavelength in the processing chamber;
The degree of dissociation of the molecular source gas is obtained from the partial pressure of the molecular source gas in the processing chamber, the emission intensity of the rare gas measured by the emission detection means, and the partial pressure of the rare gas in the processing chamber. Computing means;
A plasma processing apparatus, comprising: process control means for controlling processing conditions based on the amount of atomic radicals predicted from the degree of dissociation obtained by the computing means.

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